Composition for dyeing keratin fibres with a cationic direct dye and a thickening polymer

ABSTRACT

The invention relates to a composition for dyeing fibers such as the hair, comprising at least one cationic direct dye of given formula, and which also contains at least one thickening polymer chosen from the group comprising:—nonionic amphiphilic polymers comprising at least one hydrophilic unit and at least one unit containing a fatty chain,—anionic amphiphilic polymers comprising at least one hydrophilic unit and at least one unit containing a fatty chain,—cationic amphiphilic polymers comprising at least one hydrophilic unit and at least one unit containing a fatty chain. The invention also relates to the dyeing processes and dyeing kits therefor.

The invention relates to a composition for dyeing keratin fibres, inparticular human keratin fibres such as the hair, comprising, in amedium which is suitable for dyeing, at least one cationic direct dye ofgiven formula and at least one specific thickening polymer.

The invention also relates to the dyeing processes and dyeing devicesusing the said composition.

Two types of dyeing may be distinguished in the haircare sector.

The first is semi-permanent or temporary dyeing, or direct dyeing, whichuses dyes capable of giving the hair a natural coloration, a more orless pronounced colour change which may withstand shampooing severaltimes. These dyes are also known as direct dyes; they can be used withor without an oxidizing agent. In the presence of an oxidizing agent,the aim is to obtain lightening dyeing. Lightening dyeing is carried outby applying a mixture, prepared at the time of use, of a direct dye andan oxidizing agent to the hair, and makes it possible in particular toobtain, by lightening the melanin in the hair, an advantageous effectsuch as a unified colour in the case of grey hair, or to bring out thecolour in the case of naturally pigmented hair.

The second is permanent dyeing or oxidation dyeing. This is carried outwith so-called “oxidation” dyes comprising oxidation dye precursors andcouplers. Oxidation dye precursors, commonly known as “oxidation bases”,are compounds which are initially colourless or weakly coloured whichdevelop their dyeing power on the hair in the presence of oxidizingagents added at the time of use, leading to the formation of colouredcompounds and dyes. The formation of these coloured compounds and dyesresults either from an oxidative condensation of the “oxidation bases”with themselves or from an oxidative condensation of the oxidation baseswith coloration-modifying compounds commonly known as “couplers”, whichare generally present in the dye compositions used in oxidation dyeing.

It is known practice to add direct dyes to oxidation dyes in order tovary the shades obtained with the said oxidation dyes or to enrich theshades with glints.

Among the cationic direct dyes available in the sector of dyeing keratinfibres, in particular human keratin fibres, the compounds whosestructure is developed in the text hereinbelow are already known;nevertheless, these dyes lead to colorations which have characteristicsthat are still unsatisfactory as regards the intensity, the homogeneityof the colour distributed along the fibre, in which case the colorationis said to be too selective, and as regards the staying power, in termsof the resistance to the various attacking factors to which the hair maybe subjected (light, bad weather, shampooing).

After considerable research conducted in this matter, the Applicant hasnow discovered that it is possible to obtain novel compositions fordyeing keratin fibres which are capable of giving more intense and yetunselective colorations which show good resistance to the variousattacking factors to which the hair may be subjected, by combining atleast one specific thickening polymer with at least one known cationicdirect dye of the prior art, which have the respective formulae definedbelow.

This discovery forms the basis of the present invention.

A first subject of the present invention is thus a composition fordyeing keratin fibres, and in particular human keratin fibres such asthe hair, containing, in a medium which is suitable for dyeing, (i) atleast one cationic direct dye whose structure corresponds to formulae(I) to (IV) defined below, characterized in that it also contains (ii)at least one specific thickening polymer.

(i) The cationic direct dye which can be used according to the presentinvention is a compound chosen from those of formulae (I), (II), (III),(III′) and (IV) below:

a) the compounds of formula (I) below:

in which:D represents a nitrogen atom or a —CH group,R₁ and R₂, which may be identical or different, represent a hydrogenatom; a C₁-C₄ alkyl radical which can be substituted with a —CN, —OH or—NH₂ radical or form, with a carbon atom of the benzene ring, aheterocycle optionally containing oxygen or nitrogen, which can besubstituted with one or more C₁-C₄ alkyl radicals; a 4′-aminophenylradical,R₃ and R′₃, which may be identical or different, represent a hydrogenatom, a halogen atom chosen from chlorine, bromine, iodine and fluorine,a cyano radical, or a C₁-C₄ alkyl, C₁-C₄ alkoxy or acetyloxy radical,X⁻ represents an anion preferably chosen from chloride, methyl sulphateand acetate,A represents a group chosen from the structures A1 to A19 below:

in which R₄ represents a C₁-C₄ alkyl radical which can be substitutedwith a hydroxyl radical and R₅ represents a C₁-C₄ alkoxy radical, withthe proviso that when D represents —CH, when A represents A₄ or A₁₃ andwhen R₃ is other than an alkoxy radical, then R₁ and R₂ do notsimultaneously denote a hydrogen atom;

b) the compounds of formula (II) below:

in which:R₆ represents a hydrogen atom or a C₁-C₄ alkyl radical,R₇ represents a hydrogen atom, an alkyl radical which can be substitutedwith a —CN radical or with an amino group, a 4′-aminophenyl radical orforms with R₆ a heterocycle optionally containing oxygen and/ornitrogen, which can be substituted with a C₁-C₄ alkyl radical,R₆ and R₉, which may be identical or different, represent a hydrogenatom, a halogen atom such as bromine, chlorine, iodine or fluorine, aC₁-C₄ alkyl or C₁-C₄ alkoxy radical or a —CN radical,X⁻ represents an anion preferably chosen from chloride, methyl sulphateand acetate,B represents a group chosen from the structures B1 to B6 below:

in which R₁₀ represents a C₁-C₄ alkyl radical, R₁₁ and R₁₂, which may beidentical or different, represent a hydrogen atom or a C₁-C₄ alkylradical;

c) the compounds of formulae (III) and (III′) below:

in which:R₁₃ represents a hydrogen atom, a C₁-C₄ alkoxy radical, a halogen atomsuch as bromine, chlorine, iodine or fluorine, or an amino radical,R₁₄ represents a hydrogen atom, a C₁-C₄ alkyl radical or forms, with acarbon atom of the benzene ring, a heterocycle optionally containingoxygen and/or substituted with one or more C₁-C₄ alkyl groups,R₁₅ represents a hydrogen atom or a halogen atom such as bromine,chlorine, iodine or fluorine,R₁₆ and R₁₇, which may be identical or different, represent a hydrogenatom or a C₁-C₄ alkyl radical,D₁ and D₂, which may be identical or different, represent a nitrogenatom or a —CH group,m=0 or 1,it being understood that when R₁₃ represents an unsubstituted aminogroup, then D₁ and D₂ simultaneously represent a —CH group and m=0,X⁻ represents an anion preferably chosen from chloride, methyl sulphateand acetate,E represents a group chosen from the structures E1 to E8 below:

in which R′ represents a C₁-C₄ alkyl radical;when m=0 and when D₁ represents a nitrogen atom, then E can also denotea group of structure E9 below:

in which R′ represents a C₁-C₄ alkyl radical;

d) the compounds of formula (IV) below:G-N═N-J  (IV)in which:the symbol G represents a group chosen from the structures G₁ to G₃below:

in which structures G₁ to G₃,R₁₈ denotes a C₁-C₄ alkyl radical, a phenyl radical which can besubstituted with a C₁-C₄ alkyl radical or a halogen atom chosen fromchlorine, bromine, iodine and fluorine;R₁₉ denotes a C₁-C₄ alkyl radical or a phenyl radical;R₂₀ and R₂₁, which may be identical or different, represent a C₁-C₄alkyl radical, a phenyl radical or together form, in G₁, a benzene ringsubstituted with one or more C₁-C₄ alkyl, C₁-C₄ alkoxy or NO₂ radicalsor together form, in G₂, a benzene ring optionally substituted with oneor more C₁-C₄ alkyl, C₁-C₄ alkoxy or NO₂ radicals;R₂₀ can also denote a hydrogen atom;Z denotes an oxygen or sulphur atom or a group —NR₁₉;M represents a —CH, —CR (R denoting C₁-C₄ alkyl) or —N⁺R₂₂(X⁻)_(r)group;K represents a —CH, —CR (R denoting C₁-C₄ alkyl) or —N⁺R₂₂(X⁻)_(r)group;P represents a —CH, —CR (R denoting C₁-C₄ alkyl) or —N⁺R₂₂(X⁻)_(r)group; r denotes zero or 1;R₂₂ represents an O⁻ anion, a C₁-C₄ alkoxy radical or a C₁-C₄ alkylradical;R₂₃ and R₂₄, which may be identical or different, represent a hydrogenatom, a halogen atom chosen from chlorine, bromine, iodine and fluorine,a C₁-C₄ alkyl or C₁-C₄ alkoxy radical or an —NO₂ radical;X⁻ represents an anion preferably chosen from chloride, iodide, methylsulphate, ethyl sulphate, acetate and perchlorate;with the proviso that,if R₂₂ denotes O⁻, then r denotes zero;if K or P or M denote C₁-C₄—N⁺-alkyl X⁻, then R₂₃ or R₂₄ is other than ahydrogen atom;if K denotes —N⁺R₂₂(X⁻)_(r), then M=P═—CH, —CR;if M denotes —N⁺R₂₂(X⁻)_(r), then K═P═—CH, —CR;if P denotes —N⁺R₂₂(X⁻)_(r), then K=M and denote —CH or —CR;if Z denotes a sulphur atom with R₂₁ denoting C₁-C₄ alkyl, then R₂₀ isother than a hydrogen atom;if Z denotes —NR₂₂ with R₁₉ denoting C₁-C₄ alkyl, then at least one ofthe radicals R₁, R₂₀ or R₂₁ of the group of structure G₂ is other than aC₁-C₄ alkyl radical;the symbol J represents:(a) a group ofstructure J₁ below:

in which structure J₁,R₂₅ represents a hydrogen atom, a halogen atom chosen from chlorine,bromine, iodine and fluorine, a C₁-C₄ alkyl or C₁-C₄ alkoxy radical, aradical —OH, —NO₂, —NHR₂₈, —NR₂₉R₃₀, —NHCO(C₁-C₄) alkyl, or forms withR₂₆ a 5- or 6-membered ring which may or may not contain one or morehetero atoms chosen from nitrogen, oxygen and sulphur;R₂₆ represents a hydrogen atom, a halogen atom chosen from chlorine,bromine, iodine and fluorine, a C₁-C₄ alkyl or C₁-C₄ alkoxy radical orforms, with R₂₇ or R₂₈, a 5- or 6-membered ring which may or may notcontain one or more hetero atoms chosen from nitrogen, oxygen andsulphur;R₂₇ represents a hydrogen atom, an —OH radical, a radical —NHR₂₈ or aradical —NR₂₉R₃₀;R₂₈ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical or a phenylradical;R₂₉ and R₃₀, which may be identical or different, represent a C₁-C₄alkyl radical, a C₁-C₄ monohydroxyalkyl radical or a C₂-C₄polyhydroxyalkyl radical;(b) a 5- or 6-membered nitrogenous heterocyclic group which can containother hetero atoms and/or carbonyl groups and which can be substitutedwith one or more C₁-C₄ alkyl, amino or phenyl radicals,and in particular a group of structure J₂ below:

in which structure J₂,R₃₁ and R₃₂, which may be identical or different, represent a hydrogenatom, a C₁-C₄ alkyl radical or a phenyl radical;Y denotes the —CO— radical or the radical

n 0 or 1, with, when n denotes 1, U denoting a —CO— radical.

In the structures (I) to (IV) defined above, the C₁-C₄ alkyl or alkoxygroup preferably denotes methyl, ethyl, butyl, methoxy or ethoxy.

The cationic direct dyes of formulae (I), (II), (III) and (III′) whichcan be used in the dye compositions in accordance with the invention areknown compounds and are described, for example, in patent applicationsWO 95/01772, WO 95/15144 and EP-A-0,714,954. Those of formula (IV) whichcan be used in the dye compositions in accordance with the invention areknown compounds and are described, for example, in patent applicationsFR-2,189,006, FR-2,285,851 and FR-2,140,205 and its Certificates ofAddition.

Among the cationic direct dyes of formula (I) which can be used in thedye compositions in accordance with the invention, mention may be mademore particularly of the compounds corresponding to the structures (I1)to (I54) below:

Among the compounds of structures (I1) to (I54) described above, theones most particularly preferred are the compounds corresponding to thestructures (I1), (I2), (I14) and (I31).

Among the cationic direct dyes of formula (II) which can be used in thedye compositions in accordance with the invention, mention may be mademore particularly of the compounds corresponding to the structures (II1)to (II9) below:

Among the cationic direct dyes of formula (III) which can be used in thedye compositions in accordance with the invention, mention may be mademore particularly of the compounds corresponding to the structures(III1) to (III18) below:

Among the specific compounds of structures (III1) to (III18) describedabove, the ones most particularly preferred are the compoundscorresponding to the structures (III4), (III5) and (III13).

Among the cationic direct dyes of formula (III′) which can be used inthe dye compositions in accordance with the invention, mention may bemade more particularly of the compounds corresponding to the structures(III′1) to (III′3) below:

Among the cationic direct dyes of formula (IV) which can be used in thedye compositions in accordance with the invention, mention may be mademore particularly of the compounds of structures (IV)₁ to (IV)₇₇ below:

The cationic direct dye(s) used according to the invention preferablyrepresent(s) from 0.001 to 10% by weight approximately relative to thetotal weight of the dye composition and even more preferably from 0.005to 5% by weight approximately relative to this weight.

(ii) The thickening polymer which can be used according to the presentinvention is chosen from the group consisting of:

-   -   (ii)₁—nonionic amphiphilic polymers comprising at least one        hydrophilic unit and at least one unit containing a fatty chain;    -   (ii)₂—anionic amphiphilic polymers comprising at least one        hydrophilic unit and at least one unit containing a fatty chain;    -   (ii)₃—cationic amphiphilic polymers comprising at least one        hydrophilic unit and at least one unit containing a fatty chain.

The nonionic amphiphilic polymers comprising at least one hydrophilicunit and at least one unit containing a fatty chain (ii)₁, usedaccording to the invention, are preferably chosen from:

(ii)₁(a) celluloses modified with groups comprising at least one fattychain; mention may be made, by way of example, of:

-   -   -   hydroxyethylcelluloses modified with groups comprising at            least one fatty chain, such as alkyl, arylalkyl or alkylaryl            groups or mixtures thereof, and in which the alkyl groups            are preferably C₈-C₂₂, such as the product Natrosol Plus            Grade 330 CS(C₁₆ alkyls) sold by the company Aqualon, or the            product Bermocoll EHM 100 sold by the company Berol Nobel,        -   hydroxyethylcelluloses modified with groups comprising at            least one polyalkylene glycol alkylphenyl ether group, such            as the product Amercell Polymer HM-1500 (polyethylene            glycol (15) nonylphenyl ether) sold by the company Amerchol.

    -   (ii)₁(b) hydroxypropylguars modified with groups comprising at        least one fatty chain, such as the product Esaflor HM 22 (C₂₂        alkyl chain) sold by the company Lamberti, and the products        Miracare XC95-3 (C₁₄ alkyl chain) and RE205-1 (C₂₀ alkyl chain)        sold by the company Rhone-Poulenc.

    -   (ii)₁(c) polyurethane ethers comprising at least one fatty chain        such as C₈-C₃₀ alkyl or alkenyl groups, for instance the        products Dapral T 210 and Dapral T 212 sold by the company Akzo.

    -   (ii)₁(d) copolymers of vinylpyrrolidone and of hydrophobic        monomers containing a fatty chain;        mention may be made, by way of example, of:        -   the products Antaron V216 or Ganex V216            (vinylpyrrolidone/hexadecene copolymer) sold by the company            I.S.P.        -   the products Antaron V220 or Ganex V220            (vinylpyrrolidone/eicosene copolymer) sold by the company            I.S.P.

    -   (ii)₁(e) copolymers of C₁-C₆ alkyl methacrylates or acrylates        and of amphiphilic monomers comprising at least one fatty chain,        such as, for example, the oxyethylenated methyl        methacrylate/stearyl acrylate copolymer sold by the company        Goldschmidt under the name Antil 208.

    -   (ii)₁(f) copolymers of hydrophilic methacrylates or acrylates        and of hydrophobic monomers comprising at least one fatty chain,        such as, for example, the polyethylene glycol        methacrylate/lauryl methacrylate copolymer.

The anionic amphiphilic polymers (ii)₂, can be chosen from those:

-   -   (ii)₂(a) comprising at least one hydrophilic unit and at least        one allyl ether unit containing a fatty chain, and preferably        from those in which the hydrophilic unit comprising an        unsaturated ethylenic anionic monomer, more particularly of a        vinylcarboxylic acid and most particularly of an acrylic acid, a        methacrylic acid or mixtures thereof, and in which the allyl        ether unit containing a fatty chain corresponds to the monomer        of formula (V) below:        CH₂═CR′CH₂OB_(n)R  (V)        in which R′ denotes H or CH₃, B denotes an ethylenoxy radical, n        is zero or denotes an integer ranging from 1 to 100, R denotes a        hydrocarbon-based radical chosen from alkyl and cycloalkyl        radicals comprising from 8 to 30 carbon atoms, preferably 10 to        24 and even more particularly from 12 to 18 carbon atoms, and        most particularly a C₁₀-C₂₄ alkyl radical.

One unit of formula (V) which is more particularly preferred accordingto the present invention is a unit in which R′ denotes H, n is equal to10 and R denotes a stearyl (C₁₈) radical.

Anionic amphiphilic polymers of this type are described and preparedaccording to an emulsion polymerization process in patent EP-0,216,479B2.

Among the said anionic amphiphilic polymers cited (ii)₂(a) it isparticularly preferred according to the invention to use the polymersformed from 20 to 60% by weight of acrylic acid and/or methacrylic acid,from 5 to 60% by weight of lower alkyl (meth)acrylates, from 2 to 50% byweight of allyl ether containing a fatty chain of formula (I), and from0 to 1% by weight of a crosslinking agent which is a well knowncopolymerizable polyethylenic unsaturated monomer, such as diallylphthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycoldimethacrylate and methylenebisacrylamide.

Among the latter polymers, the ones most particularly preferred are thecrosslinked terpolymers of methacrylic acid, of ethyl acrylate, ofpolyethylene glycol (10 EO) stearyl ether (Steareth-10), in particularthose sold by the company Allied Colloids under the names Salcare SC 80and Salcare SC 90 which are aqueous 30% emulsions of a crosslinkedterpolymer of methacrylic acid, of ethyl acrylate and of Steareth-10allyl ether (40/50/10).

The anionic amphiphilic polymers (ii)₂ can also be chosen from those:

-   -   (ii)₂(b) comprising at least one hydrophilic unit of unsaturated        olefinic carboxylic acid type, and at least one unit containing        a fatty chain exclusively of (C₁₀-C₃₀)alkyl ester of unsaturated        carboxylic acid type, and preferably from those in which the        hydrophilic unit of unsaturated olefinic carboxylic acid type        corresponds to the monomer of formula (VI) below:        in which formula R¹ denotes H or CH₃ or C₂H₅, i.e. acrylic acid,        methacrylic acid or ethacrylic acid units, and in which the unit        containing a fatty chain of (C₁₀-C₃₀)alkyl ester of unsaturated        carboxylic acid type corresponds to the monomer of formula (VII)        below:        in which formula R¹ denotes H or CH₃ or C₂H₅ (i.e. acrylate,        methacrylate or ethacrylate units) and preferably H (acrylate        units) or CH₃ (methacrylate units), R² denoting a C₁₀-C₃₀ alkyl        and preferably C₁₂-C₂₂ alkyl radical.

(C₁₀-C₃₀)alkyl esters of unsaturated carboxylic acids in accordance withthe invention comprise, for example, lauryl acrylate, stearyl acrylate,decyl acrylate, isodecyl acrylate, dodecyl acrylate and thecorresponding methacrylates, lauryl methacrylate, stearyl methacrylate,decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.

Anionic amphiphilic polymers of this type (ii)₂(b) are described andprepared, for example, according to U.S. Pat. Nos. 3,915,921 and4,509,949.

Anionic amphiphilic polymers (ii)₂(b) which can be used in the contextof the present invention can more particularly denote polymers formedfrom a mixture of monomers comprising:

-   (i) essentially acrylic acid and an ester of formula (VII) described    above in which R¹ denotes H or CH₃, R² denoting an alkyl radical    containing from 12 to 22 carbon atoms, and a crosslinking agent,    such as, for example, those comprising 95 to 60% by weight of    acrylic acid (hydrophilic unit), 4 to 40% by weight of C₁₀-C₃₀ alkyl    acrylate (unit containing a fatty chain) and 0 to 6% by weight of    crosslinking polymerizable monomer, or 98 to 96% by weight of    acrylic acid (hydrophilic unit), 1 to 4% by weight of C₁₀-C₃₀ alkyl    acrylate (unit containing a fatty chain) and 0.1 to 0.6% by weight    of crosslinking polymerizable monomer,-   (ii) essentially acrylic acid and lauryl methacrylate, such as the    polymer formed from 66% by weight of acrylic acid and 34% by weight    of lauryl methacrylate.

The said crosslinking agent is a monomer containing a group

with at least one other polymerizable group whose unsaturated bonds arenot conjugated to each other. Mention may be made in particular ofpolyallyl ethers such as, in particular, polyallylsucrose andpolyallylpentaerythritol.

Among the said polymers cited in class (ii)₂(b), the ones mostparticularly preferred according to the present invention are theproducts sold by the company Goodrich under the trade names Pemulen TR1,Pemulen TR2, Carbopol 1382 and even more preferably Pemulen TR1 and theproduct sold by the company S.E.P.C. under the name Coatex SX.

The cationic amphiphilic polymers (ii)₃ used according to the inventionare preferably chosen from quaternized cellulose derivatives andpolyacrylates containing amino side groups.

The quaternized cellulose derivatives are, in particular,

-   -   (ii)₃(a) quaternized celluloses modified with groups comprising        at least one fatty chain, such as alkyl, arylalkyl or alkylaryl        groups comprising at least 8 carbon atoms, or mixtures thereof,    -   (ii)₃(b) quaternized hydroxyethylcelluloses modified with groups        comprising at least one fatty chain, such as alkyl, arylalkyl or        alkylaryl groups comprising at least 8 carbon atoms, or mixtures        thereof.

The polyacrylates containing amino side groups (ii)₃(c), which may ormay not be quaternized, contain, for example, hydrophobic groups such asSteareth-20 [polyoxyethylenated (20) stearyl alcohol].

The alkyl radicals borne by the above quaternized celluloses orhydroxycelluloses preferably comprise from 8 to 30 carbon atoms.

The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthrylgroups.

As examples of quaternized alkylhydroxyethyl-celluloses containingC₈-C₃₀ fatty chains, mention may be made of the products QuatrisoftLM200, Quatrisoft LM-X529-18-A, Quatrisoft LM-X529-18-B. (C₁₂ alkyl) andQuatrisoft LM-X529-8 (C₁₈ alkyl) sold by the company Amerchol and theproducts Crodacel QM, Crodacel QL (C₁₂ alkyl) and Crodacel QS (C₁₈alkyl) sold by the company Croda.

As examples of polyacrylates containing amino side chains, mention maybe made of the polymers 8781-124B or 9492-103 from the company NationalStarch.

It is more particularly preferred, according to the present invention,to use the amphiphilic polymers of nonionic type (ii)₁ and of anionictype (ii)₂ described above and even more particularly the amphiphilicpolymers of class (ii)₁(a) and (ii)₂(c) and of class (ii)₂(a) and(ii)₂(b).

The amphiphilic thickening polymers of nonionic, anionic or cationictype used in the compositions of the present invention are preferablypresent in a proportion of from 0.01 to 10% by weight approximately, inparticular in a proportion of from 0.1 to 5% by weight approximately,relative to the total weight of the dye composition applied to thekeratin fibres.

The medium which is suitable for dyeing (or support) generallycomprising water or of a mixture of water and at least one organicsolvent to dissolve the compounds which would not be sufficientlywater-soluble. As organic solvents, mention may be made, for example, ofC₁-C₄ lower alkanols such as ethanol and isopropanol; aromatic alcoholssuch as benzyl alcohol, as well as similar products and mixturesthereof.

The solvents can be present in proportions preferably of between 1 and40% by weight approximately relative to the total weight of the dyecomposition, and even more preferably between 5 and 30% by weightapproximately.

The pH of the dye composition in accordance with the invention isgenerally approximately between 2 and 11 and preferably approximatelybetween 5 and 10. It can be adjusted to the desired value usingacidifying or basifying agents usually used for dyeing keratin fibres.

Among the acidifying agents, mention may be made, by way of example, ofinorganic or organic acids such as hydrochloric acid, orthophosphoricacid, sulphuric acid, carboxylic acids such as acetic acid, tartaricacid, citric acid and lactic acid, and sulphonic acids.

Among the basifying agents, mention may be made, by way of example, ofaqueous ammonia, alkaline carbonates, alkanolamines such as mono-, di-and triethanolamine and derivatives thereof, sodium hydroxide, potassiumhydroxide and the compounds of formula (VIII) below:

in which W is a propylene residue optionally substituted with a hydroxylgroup or a C₁-C₆ alkyl radical; R₃₃, R₃₄, R₃₅ and R₃₆, which may beidentical or different, represent a hydrogen atom or a C₁-C₆ alkyl orC₁-C₆ hydroxyalkyl radical.

In addition to the cationic direct dye(s) (i) defined above, the dyecomposition in accordance with the invention can contain one or moreadditional direct dyes which can be chosen, for example, fromnitrobenzene dyes, anthraquinone dyes, naphthoquinone dyes,triarylmethane dyes, xanthene dyes and azo dyes which are non-cationic.

When it is intended for oxidation dyeing, the dye composition inaccordance with the invention contains, in addition to the cationicdirect dye(s) (i), one or more oxidation bases chosen from the oxidationbases conventionally used for oxidation dyeing and among which mentionmay be made in particular of para-phenylenediamines,bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenots andheterocyclic bases.

When they are used, the oxidation base(s) preferably represent(s) from0.0005 to 12% by weight approximately relative to the total weight ofthe dye composition, and even more preferably from 0.005 to 6% by weightapproximately relative to this weight.

When it is intended for oxidation dyeing, the dye composition inaccordance with the invention can also contain, in addition to thecationic direct dye (i) and the thickening polymer (ii) as well as theoxidation bases, one or more couplers so as to modify the shadesobtained or to enrich them with glints, by using the cationic directdye(s) (i) and the oxidation base(s).

The couplers which can be used in the dye composition in accordance withthe invention can be chosen from the couplers used conventionally inoxidation dyeing and among which mention may be made in particular ofmeta-phenylenediamines, meta-aminophenols, meta-diphenols andheterocyclic couplers.

When it is (they are) present, the coupler(s) preferably represent(s)from 0.0001 to 10% by weight approximately relative to the total weightof the dye composition, and even more preferably from 0.005 to 5% byweight approximately relative to this weight.

The dye composition in accordance with the invention can also containvarious adjuvants conventionally used in compositions for dyeing thehair, such as antioxidants, penetrating agents, sequestering agents,fragrances, buffers, dispersing agents, surfactants, film-formingagents, ceramides, preserving agents, screening agents and opacifiers.

Needless to say, a person skilled in the art will take care to selectthis (these) optional complementary compound(s) such that theadvantageous properties intrinsically associated with the dyecomposition in accordance with the invention are not, or are notsubstantially, adversely affected by the addition(s) envisaged.

The dye composition according to the invention can be in various forms,such as in the form of liquids, shampoos, creams or gels or any otherform which is suitable for dyeing keratin fibres, and in particularhuman hair. It can be obtained by mixing, at the time of use, acomposition, which may be pulverulent, containing the cationic directdye(s) with a composition containing the specific thickening polymer.

When the combination of the cationic direct dye (i) and the thickeningpolymer (ii) according to the invention is used in a compositionintended for oxidation dyeing (in which case one or more oxidation basesare used, optionally in the presence of one or more couplers) or when itis used in a composition intended for lightening direct dyeing, then thedye composition in accordance with the invention also comprises at leastone oxidizing agent chosen, for example, from hydrogen peroxide, ureaperoxide, alkali metal bromates, persalts such as perborates andpersulphates, and enzymes such as peroxidases, lactases and two-electronoxidoreductases. It is particularly preferred to use hydrogen peroxideor enzymes.

Another subject of the invention is a process for dyeing keratin fibres,and in particular human keratin fibres such as the hair, using the dyecomposition as defined above.

According to a first variant of this dyeing process in accordance withthe invention, at least one dye composition as defined above is appliedto the fibres, for a period which is sufficient to develop the desiredcoloration, after which the fibres are rinsed, optionally washed withshampoo, rinsed again and dried.

The time required to develop the coloration on the keratin fibres isgenerally between 3 and 60 minutes and even more specifically between 5and 40 minutes.

According to a second variant of this dyeing process in accordance withthe invention, at least one dye composition as defined above is appliedto the fibres, for a period which is sufficient to develop the desiredcoloration, without final rinsing.

According to one specific embodiment of this dyeing process, and whenthe dye composition in accordance with the invention comprises at leastone oxidation base and at least one oxidizing agent, the dyeing processcomprises a first step which consists in separately storing, on the onehand, a composition (A1) comprising, in a medium which is suitable fordyeing, at least one cationic direct dye (i) as defined above and atleast one oxidation base, and, on the other hand, a composition (B1)comprising, in a medium which is suitable for dyeing, at least oneoxidizing agent, and then in mixing them together at the time of use,after which this mixture is applied to the keratin fibres, thecomposition (A1) or the composition (B1) containing the thickeningpolymer (ii) as defined above.

According to another specific embodiment of this dyeing process, andwhen the dye composition in accordance with the invention comprises atleast one oxidizing agent, the dyeing process comprises a first stepwhich consists in separately storing, on the one hand, a composition(A2) comprising, in a medium which is suitable for dyeing, at least onecationic direct dye (i) as defined above, and, on the other hand, acomposition (B2) comprising, in a medium which is suitable for dyeing,at least one oxidizing agent, and then in mixing them together at thetime of use, after which this mixture is applied to the keratin fibres,the composition (A2) or the composition (B2) containing the thickeningpolymer as defined above.

Another subject of the invention is a multi-compartment dyeing device ordyeing “kit” or any other multi-compartment packaging system, a firstcompartment of which comprises the composition (A1) or (A2) as definedabove and a second compartment of which comprises the composition (B1)or (B2) as defined above. These devices can be equipped with means fordispensing the desired mixture onto the hair, such as the devicesdescribed in patent FR 2,586,913 in the name of the Applicant.

The examples which follow are intended to illustrate the inventionwithout, however, limiting its scope.

EXAMPLES Examples 1 to 3

The three direct dyeing compositions given in the table below wereprepared: (all contents expressed in grams) Example Example Example 1 23 Cationic direct dye of 0.2 formula (I1) Cationic direct dye of 0.2formula (I14) Cationic direct dye of 0.1 formula (IV27) Diurethane (HMD)of oxy- 1.0 AM* ethylenated (66 EO) and oxy- propylenated (14 PO)C₁₆-C₁₈ alcohols, sold under the name Dapral T212 by the company AkzoMethacrylic acid/ethyl 1.0 AM* acrylate/Steareth 10 allyl ethercrosslinked terpolymer sold as a 30% by weight emulsion under the nameSalcare SC90 by the company Allied Colloid Acrylic acid/C₁₀-C₃₀ alkyl1.0 AM* acrylate crosslinked copolymer sold under the name Pemulen TR1by the company Goodrich Ethanol 10 10 10 2-Amino-2-methyl-1-propanol pH9 pH 9 pH 9 qs Demineralized water qs 100 100 100AM* denotes active material

The above compositions were each applied for 30 minutes to locks ofnatural grey hair containing 90% white hairs. The locks of hair werethen rinsed, washed with a standard shampoo and then dried.

were dyed in the following shades: Examples Shades obtained 1 Bright red2 Bright orange 3 Bright purple

1. A ready-to-use composition for dyeing fibers, comprising: (i) atleast one cationic direct dye chosen from compounds of formulae (I),(II), (III), (III′) and (IV) below, and (ii) at least one thickeningpolymer; (a) wherein said compounds of formula (I) are chosen fromcompounds of formula:

in which: D is chosen from a nitrogen atom and a —CH group, R₁ and R₂,which may be identical or different, are chosen from a hydrogen atom; a4′-aminophenyl radical; and C₁-C₄ alkyl radicals which can optionally besubstituted with a radical chosen from —CN, —OH and —NH₂ radicals orform, with each other or a carbon atom of the benzene ring of formula(I), a heterocycle optionally containing a heteroatom chosen from oxygenand nitrogen, which can be substituted with at least one radical chosenfrom C₁-C₄ alkyl radicals; R₃ and R′₃, which may be identical ordifferent, are chosen from a hydrogen atom, halogen atoms, a cyanoradical, C₁-C₄ alkyl radicals, C₁-C₄ alkoxy radicals and acetyloxyradicals, X⁻ is chosen from anions, A is chosen from structures A₁ toA₁₉ below:

in which: R₄ is chosen from C₁-C₄ alkyl radicals which can besubstituted with a hydroxyl radical, and R₅ is chosen from C₁-C₄ alkoxyradicals, and wherein when D represents —CH, when A represents A₄ or A₁₃and when R₃ is not an alkoxy radical, R₁ and R₂ are not both a hydrogenatom; (b) wherein said compounds of formula (II) are chosen fromcompounds of formula:

in which: R₆ is chosen from a hydrogen atom and C₁-C₄ alkyl radicals, R₇is chosen from a hydrogen atom, alkyl radicals which can be substitutedwith a species chosen from a —CN radical and an amino group, and a4′-aminophenyl radical, or forms, with R₆, a heterocycle optionallycomprising at least one heteroatom chosen from oxygen and nitrogen,which can be substituted with C₁-C₄ alkyl radicals, R₈ and R₉, which maybe identical or different, are chosen from a hydrogen atom, halogenatoms, C₁-C₄ alkyl radicals C₁-C₄ alkoxy radicals and a —CN radical, X⁻is chosen from anions, B is chosen from structures B₁ to B₆ below:

in which: R₁₀ is chosen from C₁-C₄ alkyl radicals, and R₁₁ and R₁₂,which may be identical or different, are chosen from a hydrogen atom andC₁-C₄ alkyl radicals; (c) wherein said compounds of formulae (III) and(III′) are chosen from compounds of formulae:

in which: R₁₃ is chosen from a hydrogen atom, C₁-C₄ alkoxy radicals,halogen atoms and an amino radical, R₁₄ is chosen from a hydrogen atom,C₁-C₄ alkyl radicals or forms, with a carbon atom of the benzene ring, aheterocycle optionally containing an oxygen heteroatom and/orsubstituted with at least one to radical chosen from C₁-C₄ alkylradicals, R₁₅ is chosen from a hydrogen atom and halogen atoms, R₁₆ andR₁₇, which may be identical or different, are chosen from a hydrogenatom and C₁-C₄ alkyl radicals, D₁ and D₂, which may be identical ordifferent, are chosen from a nitrogen atom and a —CH group, m=0 or 1,wherein when R₁₃ is an unsubstituted amino group, D₁ and D₂ are both agroup and m=0, X⁻ is chosen from anions, E is chosen from structures E₁to E₈ below:

in which R′ is chosen from C₁-C₄ alkyl radicals; wherein when m=0 andwhen D₁ represents a nitrogen atom, E can be further chosen fromstructure E9 below:

in which R′ is chosen from C₁-C₄ alkyl radicals; (d) wherein saidcompounds of formula (IV) are chosen from compounds of formula:G-N═N-J  (IV) in which: G is chosen from structures G₁ to G₃ below:

in which: R₁₈ is chosen from C₁-C₄ alkyl radicals and a phenyl radicalwhich can optionally be substituted with C₁-C₄ alkyl radicals or ahalogen atom chosen from chlorine, bromine, iodine and fluorine; R₁₉ ischosen from C₁-C₄ radicals and a phenyl radical; R₂₀ and R₂₁, which maybe identical or different, are chosen from C₁-C₄ alkyl radicals and aphenyl radical, or together form, in G₁, a benzene ring substituted withat least one radical chosen from C₁-C₄ alkyl radicals, C₁-C₄ alkoxyradicals and NO₂ radicals, or together form, in G₂, a benzene ringoptionally substituted with at least one radical chosen from C₁-C₄ alkylradicals, C₁-C₄ alkoxy radicals and NO₂ radicals; R₂₀ can be furtherchosen from a hydrogen atom; Z is chosen from an oxygen atom, a sulphuratom and —NR₁₉ radicals; M is chosen from a —CH radical, —C(C₁-C₄ alkyl)radicals and —N⁺R₂₂(X⁻)_(r) radicals; K is chosen from a —CH radical,—C(C₁-C₄ alkyl) radicals and —N⁺R₂₂(X⁻)_(r) radicals; P is chosen from a—CH radical, —C(C₁-C₄ alkyl) radicals and —N⁺R₂₂(X⁻)_(r) radicals;wherein r denotes zero or 1; wherein R₂₂ is chosen from an O⁻ anion,C₁-C₄ alkoxy radicals, and C₁-C₄ alkyl radicals; R₂₃ and R₂₄, which maybe identical or different, are chosen from a hydrogen atom, halogenatoms chosen from chlorine, bromine, iodine and fluorine, C₁-C₄ alkylradicals, C₁-C₄ alkoxy radicals and an —NO₂ radical; X⁻ is chosen fromanions; wherein if R₂₂ is O⁻, r is zero; wherein if K or P or M isC₁-C₄—N⁺-alkyl X⁻, either R₂₃ or R₂₄ is not a hydrogen atom; wherein ifK is —N⁺R₂₂(X⁻)_(r), M and P are the same and are chosen from a —CHradical and —C(C₁-C₄ alkyl) radicals; wherein if M denotes—N⁺R₂₂(X⁻)_(r), K and P are the same and are chosen from a —CH radicaland —C(C₁-C₄ alkyl) radicals; if P is —N⁺R₂₂(X⁻)_(r), K and M are thesame and are chosen from a —CH radical and —C(C₁-C₄ alkyl) radicals; ifZ is a sulphur atom with R₂₁ being a radical chosen from C₁-C₄ alkylradicals, R₂₀ is not a hydrogen atom; if Z is —NR₂₂ with R₁₉ being aradical chosen from C₁-C₄ alkyl radicals, at least one of the radicalsR₁₈, R₂₀ and R₂₁ of G₂ is not chosen from C₁-C₄ alkyl radicals; J ischosen from: (1) radicals chosen from structure J₁ below:

in which: R₂₅ is chosen from a hydrogen atom, halogen atoms chosen fromchlorine, bromine, iodine and fluorine, C₁-C₄ alkyl radicals, C₁-C₄alkoxy radicals, an —OH radical, an —NO₂ radical, —NHR₂₈ radicals,—NR₂₉R₃₀ radicals, —NHCO(C₁-C₄) alkyl radicals, or forms, with R₂₆, a 5-or 6-membered ring optionally containing at least one heteroatom chosenfrom nitrogen, oxygen and sulphur; R₂₆ is chosen from a hydrogen atom,halogen atoms chosen from chlorine, bromine, iodine and fluorine, C₁-C₄alkyl radicals, C₁-C₄ alkoxy radicals or forms, with R₂₇ or R₂₈, a 5- or6-membered ring optionally containing at least one heteroatom chosenfrom nitrogen, oxygen and sulphur; R₂₇ is chosen from a hydrogen atom,an —OH radical, —NHR₂₈ radicals and —NR₂₉R₃₀ radicals; R₂₈ is chosenfrom a hydrogen atom, C₁-C₄ alkyl radicals, C₁-C₄ monohydroxyalkylradicals, C₂-C₄ polyhydroxyalkyl radicals and a phenyl radical; R₂₉ andR₃₀, which may be identical or different, are chosen from C₁-C₄ alkylradicals, C₁-C₄ monohydroxyalkyl radicals and C₂-C₄ polyhydroxyalkylradicals; (2) 5- and 6-membered nitrogenous heterocyclic groupsoptionally containing other heteroatoms and/or carbonyl groups andoptionally substituted with at least one radical chosen from C₁-C₄ alkylradicals, an amino radical, a phenyl radical, and wherein said at leastone thickening polymer is chosen from polymers comprising:(ii)₁—nonionic amphiphilic polymers, comprising: at least onehydrophilic unit and at least one unit comprising a fatty chain;(ii)₂—anionic amphiphilic polymers, comprising: at least one hydrophilicunit and at least one unit comprising a fatty chain; and (ii)₃—cationicamphiphilic polymers, comprising at least one hydrophilic unit and atleast one unit comprising a fatty chain.